Synthesis and crystal structures of cationic lanthanide(III) monoporphyrinate complexes

Abstract

Reactions of an excess of Ln[N(SiMe₃)₂]₃·x[LiCl(THF)₃], generated in situ from the reaction of anhydrous LnCl₃ with 3 equivalents of Li[N(SiMe₃)₂] in tetrahydrofuran, with 5,10,15,20-tetrakis(p-methoxyphenyl)porphyrin (H₂TMPP) in refluxing tetrahydrofuran–bis(2-methoxyethyl) ether solution (1∶6 v/v) gave the cationic monoporphyrinate complexes [Ln^III(TMPP)(H₂O)₃]Cl (Ln = Yb; 1, Er, 2, or Y 3), and with 5,10,15,20-tetrakis(p-tolyl)porphyrin (H₂TTP) gave [Yb^III(TTP)(H₂O)₂(THF)]Cl 4. The structures of compounds 1–4 have been established by X-ray crystallography. Metathesis of 1 with an excess of AgBF₄ gave the unexpected neutral monoporphyrinate complex [Ag^II(TMPP)] 5 whose structure was also determined. Compound 1 catalysed the cyclotrimerization of phenyl isocyanate.